The present invention relates to multiblock interpolymers of conjugated diene and monovinyl aromatic monomer and processes for the preparation thereof. More particularly, the present invention relates to multiblock interpolymers having the following symmetric structures:
Y-X-Y 
wherein Y represents a block of a random copolymer of conjugated diene and monovinyl aromatic monomer; and
X represents a block of butadiene homopolymer, a block of isoprene homopolymer, or a block of butadiene/isoprene copolymer.
Generally, representative block interpolymers based on butadiene, isoprene and styrene are SBS and SIS, wherein SBS is butadiene/styrene triblock copolymers (wherein B represents polybutadiene block and S represents polystyrene block), and SIS is isoprene/styrene triblock copolymers (wherein I represents polyisoprene block and S represents polystyrene block). By employing difunctional lithium based initiators and changing the charging orders of butadiene, isoprene and styrene, block interpolymers having various different structures can be obtained. Such block interpolymers comprise those having the following symmetric structures: (1) S-I-B-I-S (wherein butadiene, isoprene and styrene are charged sequentially); (2) S-B-I-B-S (wherein isoprene, butadiene and styrene are charged sequentially); (3) S-I-BI-B-BI-I-S (wherein butadiene and isoprene are charged simultaneously at first, and then styrene is charged); (4) S-BS-B-I-B-BS-S (wherein isoprene is charged at first, and then butadiene and styrene are charged simultaneously); (5) S-IS-I-B-I-IS-S (wherein butadiene is charged at first, and then isoprene and styrene are charged simultaneously); (6) S-IS-I-BI-I-BI-I-IS-S (wherein butadiene, isoprene and styrene are charged simultaneously), in the above formula, S represents a polystyrene block, B represents a polybutadiene block, I represents a polyisoprene block, BI represents a block of tapered copolymer of butadiene and isoprene, BS represents a block of tapered copolymer of butadiene and styrene, and IS represents a block of tapered copolymer of isoprene and styrene.
U.S. Pat. No. 5,100,965 to Hsu et al. disclosed a process to synthesize polymers having high trans microstructure content of about 60% to about 85%. The polymers obtained therefrom include high trans-1,4-polybutadiene, styrene-isoprene-butadiene terpolymers with high trans-1,4-polybutadiene microstructure, high trans-isoprene-butadiene copolymers and styrene-butadiene copolymers having high trans-1,4-polybutadiene microstructure. As is know in the art, trans-1,4-polybutadiene is not a rubber, but a thermoplastic resin by virtue of its high level of crystallinity. The high trans styrene-butadiene, styrene-isoprene-butadiene, isoprene-butadiene copolymers prepared by the process in ""965 patent all have high level of crystalline structure and have melting points within the range of about xe2x88x9220xc2x0 C. to about 40xc2x0 C. As stated in column 13 of ""965 patent, though the segmented copolymers of its invention can be used to make tire tread compounds without the need to blend additional rubbers therein, it is desirable, in many cases, to blend the segmented copolymers with one or more additional rubbers, such as natural rubber or styrene-butadiene rubber, to attain the desired performance characteristics for the tire tread compound, such as good rolling resistance, tear resistance, traction, tread wear characteristics and low temperature properties. In fact, such kind of material is seldom used alone as tire rubber. Also the glass transition temperature of the high trans styrene-butadiene, styrene-isoprene-butadiene, isoprene-butadiene copolymers prepared by the process in ""965 patent is from about xe2x88x9260xc2x0 C. to about xe2x88x9295xc2x0 C. varying with their monomeric makeup. Such kind of materials cannot be of wide glass transition zone, instead, exhibit narrow glass transition zone. It is well known that wide glass transition zone is indicative of an integrated rubber of excellent property balance.
The preparation process disclosed ""965 patent needs to utilize a composite initiating system of complicated composition. Besides at least one organolithium initiator, an organoaluminum compound, a barium alkoxide and a lithium alkoxide are necessarily used in the initiating system.
U.S. Pat. No. 5,070,148 to Hsu et al. disclosed a rubber polymer for use in making tire treads, which is prepared by utilizing organo monolithium compounds. The rubber polymer is only a two-segment copolymer and of asymmetric structure. As stated in the patent, the object of its invention is to provide a tire tread material exhibiting excellent combination of wet skid resistance and low rolling resistance that is highly desirable for tires. It is well known in the art that low tan delta value at 60xc2x0 C. is indicative of good rolling resistance of tire treads and high tan delta value at 0xc2x0 C. is indicative of good traction characteristic (wet skid resistance). The loss angle tan delta at 60xc2x0 C. reported in Example 1 of the ""148 patent is 0.130; its loss angle tan delta at 0xc2x0 C. reported in Example 1 is 0.306.
The object of the present invention is to provide novel multiblock interpolymers of conjugated diene and monovinyl aromatic monomer, which have in the same molecule both a rubber block of random copolymer of conjugated diene and monovinyl aromatic monomer and a rubber block selected from blocks of butadiene homopolymer, isoprene homopolymer and butadiene/isoprene copolymer, and hence possess excellent properties of the both two kinds of rubbers.
The inventive multiblock interpolymers are energy-saving rubber materials for using as tire tread rubber, which have very low loss angle tan delta value at 60xc2x0 C. and thus undergo very low energy loss. Also, such multiblock interpolymers all exhibit wide glass transition zone indicative of an integrated rubber of excellent property balance. Further, such multiblock interpolymers contain no considerable crystalline structure and thus can be used alone as tire tread materials, without the need to blend with one or more additional rubbers to attain desired property balance. The present inventive rubber materials have excellent balance of good wet skid resistance and very low rolling resistance, as well as good low temperature properties, and thus are integrated rubber of excellent comprehensive properties.
Another object of the present invention is to provide processes for the preparation of the novel multiblock interpolymers, it can prepare the above integrated rubber material in situ in a single reactor instead of physically blending.
The present preparation process utilizes simple one-component initiating system, without the need of adding other components, such as an organoaluminum compound, a barium alkoxide and a lithium alkoxide, as coinitiator.
Therefore, in one aspect the present invention relates to multiblock interpolymers having the following symmetric structures:
Y-X-Y 
wherein Y represents a block of a random copolymer conjugated diene and monovinyl aromatic monomer, wherein the content of the 1,2- or 3,4-addition polymerization structure of the conjugated diene in block Y is from 10 to 50 percent by weight, based on the total weight of the units derived from the conjugated diene in block Y; and
X represents a block of butadiene homopolymer, a block of isoprene homopolymer, or a block of butadiene/isoprene copolymer, wherein the content of 3,4-addition polymerization structure of isoprene in block X is, based on the total weight of the units derived from the isoprene in block X, from 6 to 20 percent by weight, and/or the content of 1,2-addition polymerization structure of butadiene in block X is, based on the total weight of the units derived from the butadiene in block X, from 6 to 20 percent by weight.
In another aspect, the present invention relates to processes for the preparation of the present multiblock interpolymers by anionic polymerization.
In still another aspect, the present invention relates to use of the present multiblock interpolymers as elastomeric materials, such as tire tread materials.
The follows will describe the present invention in detail.
In the present multiblock interpolymers, block X is a block of butadiene homopolymer, a block of isoprene homopolymer, or a block of butadiene/isoprene copolymer. Preferably, block X is a block having the following structure:
-B- or
-I-or
-I-B-I- or
-B-I-B or
-I-BI-B-BI-I-,
wherein B represents a block of butadiene homopolymer, I represents a block of isoprene homopolymer, and BI represents a block of tapered copolymer of butadiene and isoprene.
Accordingly, the present multiblock interpolymers preferably are of the following structure;
Y-B-Y or
Y-I-Y or
Y-I-B-I-Y or
Y-B-I-B-Y or
Y-I-BI-B-BI-I-Y.
In block X, the content of 1,2-addition polymerization structure of the butadiene is preferably in the range of from 6 to 35 percent by weight, more preferably from 10 to 20 percent by weight, based on the total weight of the units derived from the butadiene in block X, and the content of 3,4-addition polymerization structure of isoprene is in the range of from 6 to 35 percent by weight, more preferably from 10 to 20 percent by weight, based on the total weight of the units derived from the isoprene in block X. When block X is a block of butadiene/isoprene copolymer, for example, when block X is -I-B-I-, -B-I-B- or -I-BI-B-BI-I, the weight ratio of butadiene to isoprene is preferably from 10/90 to 90/10, more preferably from 30/70 to 70/30.
In the present multiblock interpolymers, block Y is a block of random copolymer of conjugated diene and monovinyl aromatic monomer. Suitable monomers are any conjugated diene and monovinyl aromatic monomer from which the random copolymer rubber block can be obtained. The conjugated diene monomer is preferably a C4-C6 conjugated diene, such as butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene, and mixtures thereof, more preferably butadiene and isoprene, most preferably butadiene. The monovinyl aromatic monomer which is preferred in block Y includes styrene or alkyl substituted styrene such as vinyl toluene (all isomers), xcex1-methylstyrene, 4-tertiary-butylstyrene, 4-methylstyrene, 3,5-diethylstyrene, 3,5-di-n-butylstyrene, 4-n-propylstyrene, 4-dodecylstyriene and mixtures thereof. More preferably, the monovinyl aromatic monomer is styrene, vinyltoluene, xcex1-methylstyrene and mixtures thereof, with styrene being most preferred. In block Y, the content of the recurring unit derived from the monovinyl aromatic monomer is generally 10 to 50 percent by weight, preferably 15 to 35 percent by weight, based on the total weight of block Y; and correspondingly, the content of the recurring unit derived from the conjugated diene is generally 50 to 90 percent by weight, preferably 65 to 85 percent by weight. In block Y, the content of 1,2- or 3,4-addition polymerization structure for the polymerized conjugated dienes is preferably 6 to 80 percent by weight, more preferably 10 to 50 percent by weight, based on the total weight of the units derived from the conjugated diene in block Y.
In the present multiblock interpolymers, the weight ratio of the total blocks Y to block X is preferably 10/90 to 90/10, more preferably 30/70 to 70/30.
Preferably, the present multiblock interpolymers have a number average molecular weight (Mn), determined by Gel Permeation Chromatography (GPC) method) of 5xc3x97104 to 35xc3x97104, and most preferably 10xc3x97104 to 25xc3x97104.
The present multiblock interpolymers can be prepared by anionic polymerization process under conventional conditions. In one preferred embodiment, the preparation process thereof comprises the steps of
a) anionic polymerizing butadiene and/or isoprene in a non-polar hydrocarbon solvent in presence of a difunctional lithium based initiator, till the butadiene and/or isoprene are polymerized completely, to form block X; and then
b) charging a mixture of conjugated diene and monovinyl aromatic monomer into the reaction mixture obtained in step a) above, continuing the anionic polymerization in presence of a polar modifier till the polymerization is complete, to form block Y.
Clearly, the present process is anionic solution polymerization process utilizing a difunctional lithium initiator to prepare a rubber polymer with symmetric block structure. The trans microstructure contents in the polybutadiene or polyisoprene obtained in the present process are roughly equal to their cis microstructure contents. As indicated above, the content of 3,4-addition polymerization structure of isoprene in block X is 6-35 percent by weight based on the total weight of the units derived from the isoprene in block X, and/or the content of 1,2-addition polymerization structure of butadiene in block X is 6-35 percent by weight based on the total weight of the units derived from the butadiene in block X; the content of the 1,2- or 3,4-addition polymerization structure of the conjugated diene in block Y is from 10-50 percent by weight based on the total weight of the units derived from the conjugated diene in block Y. Thus the present multiblock interpolymers cannot have a trans microstructure content as high as that in ""965 patent. In particular, its trans microstructure content therein is not more than 55 percent by weight; its cis microstructure content therein is not more than 39 percent by weight, with the remaining microstructure being 1,2- and/or 3,4- addition polymerization structure. The present multiblock interpolymers thus contain no considerable crystalline structure (no detectable melting points) and can be used alone as tire tread materials, without the need to blend with one or more additional rubbers to attain desired property balance.
Depending on the specific structure of block X, step a) of the present process can particularly be: (1) when block X is -B-, butadiene is polymerized in step a); (2) when block X is -I-, isoprene is polymerized in step a); (3) when block X is -I-B-I-, in step a) butadiene is first polymerized completely, and then isoprene is charged and polymerized completely; (4) when block X is -B-I-B-, in step a) isoprene is first polymerized completely, and then butadiene is charged and polymerized completely; (5) when block X is -I-BI-B-BI-I-, in step a) a mixture of butadiene and isoprene is charged to a non-polar hydrocarbon solvent and polymerized completely.
More particularly, the multiblock interpolymer Y-B-Y of the present invention can be prepared as follows. Butadiene, in an amount to provide the desired composition of the final interpolymer, is charged to a non-polar hydrocarbon solvent in a reactor, optionally a polar modifier is charged depending upon the desired microstructure of polybutadiene, and the kind and amount of the polar modifier is dependent on the desired content of 1,2-addition polymerization structure in the polybutadiene block -B-. The monomer concentration is 10 to 20 percent by weight. After the initiating temperature, which is generally about 30 to 80xc2x0 C., is reached, a difunctional lithium based initiator is charged in an amount to provide the desired molecular weight of the interpolymer. The difunctional lithium based initiator can be a single difunctional lithium based initiator or a mixture of several difunctional lithium based initiators, and generally is at least one selected from the group consisting of bislithiums derived from dihalogenated alkanes and oligomeric bislithiums thereof, bislithiums of naphthalene, and bislithiums derived from diene compounds and oligomeric bislithiums thereof. After the butadiene is polymerized completely, a mixture of conjugated diene and monovinyl aromatic monomer containing a polar modifier is charged to the reactor to prepare block Y, the conjugated diene and the monovinyl aromatic monomer are used in such amounts to provide the desired weight ratio of the conjugated diene to the monovinyl aromatic monomer in block Y. The object of use of the polar modifier is to adjust the copolymerization reactivity ratio of the conjugated diene to the monovinyl aromatic monomer, achieve the random copolymerization of the conjugated diene and the monovinyl aromatic monomer, and obtain the random copolymer block Y. The polar modifier shall be used in an amount sufficiently to make the conjugated diene and the monovinyl aromatic monomer copolymerize randomly, and the amount of the polar modifier used can be varied within a wide range depending upon the kind of the polar modifier employed. After the conjugated diene and the monovinyl aromatic monomer are polymerized completely, the polymerization is terminated and the resulted polymer product is recovered in conventional ways.
More particularly, the multiblock interpolymer Y-I-Y of the present invention can be prepared as follows. Isoprene, in an amount to provide the desired composition of the final interpolymer, is charged to a non-polar hydrocarbon solvent in a reactor, optionally a polar modifier is charged depending upon the desired microstructure of polyisoprene, and the kind and amount of the polar modifier is dependent on the desired content of 3,4-addition polymerization structure in the polyisoprene block -I-. The monomer concentration is 10 to 20 percent by weight. After the initiating temperature, which is generally about 30 to 80xc2x0 C., is reached, a difunctional lithium based initiator is charged in an amount to provide the desired molecular weight of the interpolymer. The difunctional lithium based initiator can be a single difunctional lithium based initiator or a mixture of several difunctional lithium based initiators, and generally is at least one selected from the group consisting of bislithiums derived from dihalogenated alkanes and oligomeric bislithiums thereof, bislithiums of naphthalene, and bislithiums derived from diene compounds and oligomeric bislithiums thereof. After the isoprene is polymerized completely, a mixture of conjugated diene and monovinyl aromatic monomer containing a polar modifier is charged to the reactor to prepare block Y, the conjugated diene and the monovinyl aromatic monomer are used in such amounts to provide the desired weight ratio of the conjugated diene to the monovinyl aromatic monomer in block Y. The object of use of the polar modifier is to adjust the copolymerization reactivity ratio of the conjugated diene to the monovinyl aromatic monomer, achieve the random copolymerization of the conjugated diene and the monovinyl aromatic monomer, and obtain the random copolymer block Y. The polar modifier shall be used in an amount sufficiently to make the conjugated diene and the monovinyl aromatic monomer copolymerize randomly, and the amount of the polar modifier used can be varied within a wide range depending upon the kind of the polar modifier employed. After the conjugated diene and the monovinyl aromatic monomer are polymerized completely, the polymerization is terminated and the resulted polymer product is recovered in conventional ways.
More particularly, the multiblock interpolymer Y-I-B-I-Y of the present invention can be prepared as follows. Butadiene, in an amount to provide the desired composition of the final interpolymer, is charged to a non-polar hydrocarbon solvent in a reactor, optionally a polar modifier is charged depending upon the desired microstructure of polybutadiene, and the kind and amount of the polar modifier is dependent on the desired content of 1,2-addition polymerization structure in the polybutadiene block -B-. The monomer concentration is 10 to 20 percent by weight. After the initiating temperature, which is generally about 30 to 80xc2x0 C., is reached, a difunctional lithium based initiator is charged, in an amount to provide the desired molecular weight of the interpolymer, to prepare block -B-. The difunctional lithium based initiator can be a single difunctional lithium based initiator or a mixture of several difunctional lithium based initiators, and generally is at least one selected from the group consisting of bislithiums derived from dihalogenated alkanes and oligomeric bislithiums thereof, bislithiums of naphthalene, and bislithiums derived from diene compounds and oligomeric bislithiums thereof. After complete polymerization of the butadiene, isoprene in suitable amount is charged to prepare block -I-. After the isoprene is polymerized completely, a mixture of conjugated diene and monovinyl aromatic monomer containing a polar modifier is charged to the reactor to prepare block Y, the conjugated diene and the monovinyl aromatic monomer are used in such amounts to provide the desired weight ratio of the conjugated diene to the monovinyl aromatic monomer in block Y. The object of use of the polar modifier is to adjust the copolymerization reactivity ratio of the conjugated diene to the monovinyl aromatic monomer, achieve the random copolymerization of the conjugated diene and the monovinyl aromatic monomer, and obtain the random copolymer block Y. The polar modifier shall be used in an amount sufficiently to make the conjugated diene and the monovinyl aromatic monomer copolymerize randomly, and the amount of the polar modifier used can be varied within a wide range depending upon the kind of the polar modifier employed. After the conjugated diene and the monovinyl aromatic monomer are polymerized completely, the polymerization is terminated and the resulted polymer product is recovered in conventional ways.
More particularly, the multiblock interpolymer Y-B-I-B-Y of the present invention can be prepared as follows. Isoprene, in an amount to provide the desired composition of the final interpolymer, is charged to a non-polar hydrocarbon solvent in a reactor, optionally a polar modifier is charged depending upon the desired microstructure of polyisoprene, and the kind and amount of the polar modifier is dependent on the desired content of 3,4-addition polymerization structure in the polyisoprene block -I-. The monomer concentration is 10 to 20 percent by weight. After the initiating temperature, which is generally about 30 to 80xc2x0 C., is reached, a difunctional lithium based initiator is charged, in an amount to provide the desired molecular weight of the interpolymer, to prepare block -I-. The difunctional lithium based initiator can be a single difunctional lithium based initiator or a mixture of several difunctional lithium based initiators, and generally is at least one selected from the group consisting of bislithiums derived from dihalogenated alkanes and oligomeric bislithiums thereof, bislithiums of naphthalene, and bislithiums derived from diene compounds and oligomeric bislithiums thereof. After complete polymerization of the isoprene, butadiene in suitable amount is charged to prepare block -B-. After the butadiene is polymerized completely, a mixture of conjugated diene and monovinyl aromatic monomer containing a polar modifier is charged to the reactor to prepare block Y, the conjugated diene and the monovinyl aromatic monomer are used in such amounts to provide the desired weight ratio of the conjugated diene to the monovinyl aromatic monomer in block Y. The object of use of the polar modifier is to adjust the copolymerization reactivity ratio of the conjugated diene to the monovinyl aromatic monomer, achieve the random copolymerization of the conjugated diene and the monovinyl aromatic monomer, and obtain the random copolymer block Y. The polar modifier shall be used in an amount sufficiently to make the conjugated diene and the monovinyl aromatic monomer copolymerize randomly, and the amount of the polar modifier used can be varied within a wide range depending upon the kind of the polar modifier employed. After the conjugated diene and the monovinyl aromatic monomer are polymerized completely, the polymerization is terminated and the resulted polymer product is recovered in conventional ways.
More particularly, the multiblock interpolymer Y-I-BI-B-BI-I-Y of the present invention can be prepared as follows. Butadiene and isoprene, in amounts respectively to provide the desired composition of the final interpolymer, are simultaneously charged to a non-polar hydrocarbon solvent in a reactor, optionally a polar modifier is charged depending upon the desired microstructure of polybutadiene and polyisoprene, and the desired length of the tapered block BI, and the kind and amount of the polar modifier is dependent on the desired content of 1,2-addition polymerization structure in the polybutadiene block and of 3,4-addition polymerization structure in the polyisoprene block. The monomer concentration is 10 to 20 percent by weight. After the initiating temperature, which is generally about 30 to 80xc2x0 C., is reached, a difunctional lithium based initiator is charged, in an amount to provide the desired molecular weight of the interpolymer. The difunctional lithium based initiator can be a single difunctional lithium based initiator or a mixture of several difunctional lithium based initiators, and generally is at least one selected from the group consisting of bislithiums derived from dihalogenated alkanes and oligomeric bislithiums thereof, bislithiums of naphthalene, and bislithiums derived from diene compounds and oligomeric bislithiums thereof. After the butadiene and isoprene are polymerized completely, a mixture of conjugated diene and monovinyl aromatic monomer containing a polar modifier is charged to the reactor to prepare block Y, the conjugated diene and the monovinyl aromatic monomer are used in such amounts to provide the desired weight ratio of the conjugated diene to the monovinyl aromatic monomer in block Y. The object of use of the polar modifier is to adjust the copolymerization reactivity ratio of the conjugated diene to the monovinyl aromatic monomer, achieve the random copolymerization of the conjugated diene and the monovinyl aromatic monomer, and obtain the random copolymer block Y. The polar modifier shall be used in an amount sufficiently to make the conjugated diene and the monovinyl aromatic monomer copolymerize randomly, and the amount of the polar modifier used can be varied within a wide range depending upon the kind of the polar modifier employed. After the conjugated diene and the monovinyl aromatic monomer are polymerized completely, the polymerization is terminated and the resulted polymer product is recovered in conventional ways.
The polar modifier suitable for the present process is at least one from the group of consisting of oxygen-, nitrogen-, sulfur-, or phosphorus-containing polar compounds and metal alkoxides, the specific examples include (1) oxygen containing compounds such as diethyl ether, tetrahydrofuran, a compound represented by R1OCH2CH2OR2 (wherein R1 and R2, being the same or different, represent an alkyl having 1 to 6 carbon atoms, preferably R1 is different from R2, for example, glycol dimethyl ether, glycol diethyl ether), a compound represented by R1OCH2CH2OCH2CH2OR2 (wherein R1 and R2, being the same or different, represent an alkyl having 1 to 6 carbon atoms, preferably R1 is different from R2, for example, diglycol dimethyl ether, diglycol dibutyl ether), and crown ether; (2) nitrogen-containing compounds such as triethylamine, tetramethyl ethylene diamine (TMEDA), dipiperidino ethane (DPE), preferably TMEDA; (3) phosphorus-containing compounds such as hexamethyl phosphoric triamide (HMPA); (4) metal alkoxides represented by ROM, wherein R represents a alkyl having 1 to 6 carbon atoms, O represents oxygen atom, and M represents an metal cation such as sodium cation (Na+) and potassium cation (K+), preferably potassium tert-butoxide and sodium tert-amyloxide.
The solvent suitable for the present process includes non-polar hydrocarbon solvents, selected from the group consisting of non-polar aromatic hydrocarbons, non-polar aliphatic hydrocarbons and mixtures thereof. Examples of the solvent include benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, mixed arene such as mixed xylene, mixed aliphatic hydrocarbon such as raffinate oil or mixtures thereof The solvent is preferably hexane, cyclohexane and raffinate oil.
The initiator useful in the present invention is a difunctional lithium based initiator, selected from the group consisting of bislithiums derived from dihalogenated alkanes and oligomeric bislithiums thereof, having the general formulae LiRLi and Li(DO)nR(DO)nLi, respectively, wherein R represents an alkylene group having from 4 to 10 carbon atoms, DO represents a conjugated diene having from 4 to 8 carbon atoms or mixtures thereof, with 1,3-butadiene and isoprene being preferred, and n represents the oligomerization degree, typically ranging from 2 to 8, preferably from 3 to 6, the bislithiums derived from dihalogenated alkanes and oligomeric bislithiums thereof are preferably 1,4-dilithiobutane, 1,2-dilithio-1,2-diphenylethane, 1,4-dilithio-1,1,4,4-tetraphenyl-butane, 1,4-dilithio-1,4-dimethyl-1,4-diphenyl-butane and isoprene oligomer-bislithiums and butadiene oligomer-bislithiums thereof, and any mixture thereof, bislithiums of naphthalene, such as dilithionaphthalene and xcex1-methyl-dilithio-naphthalene and mixture thereof; and bislithiums derived from diene compounds and oligomeric bislithiums thereof, for example, 1,3-phenylene-bis[3-methyl-1-(4-methyl)-phenylpentylidene]bislithium, 1,3-phenylene-bis[3-methyl-1-(4-methyl)phenyl-pentylidene]butadiene oligomer-bislithium, 1,3-phenylene-bis[3-methyl-1-(4-methyl)phenylpentylidene] isoprene oligomer-bislithium, 1,4-phenylene-bis[3-methyl-1-(4-methyl) phenylpentylidene]bis-lithium, 1,4-phenylene-bis[3-methyl-1-(4-methyl) phenylpentylidene]butadiene oligomer-bislithium, and 1, 4-phenylene-bis[3-methyl-1-(4-methyl)phenyl-pentylidene]isoprene oligomer-bislithium, and any mixture thereof.
The amount of the initiator used depends on the desired molecular weight of the multiblock interpolymers. In the present invention, the difunctional lithium based initiator is preferably used in such an amount that the multiblock interpolymers have a number average molecular weight of 5xc3x97104 to 35xc3x97104.
Optionally, conventional additives and fillers, such as antioxidant, can be added into the present multiblock interpolymers, for example Irganox 1010 (trade name, available from Ciba-Geigy AG, Switzerland) and ANTIGENE BHT (trade name, 2,6-di-tertiary-butyl-4-methylphenol, available from Sumitomo Chemical Co., Ltd., Japan) and mixture thereof.
The present invention is further illustrated by the following examples, which shall not be construed as limited.